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EP0737241B1 - Procede de fabrication d'un activateur de blanchiment au lactame contenant des particules - Google Patents

Procede de fabrication d'un activateur de blanchiment au lactame contenant des particules Download PDF

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Publication number
EP0737241B1
EP0737241B1 EP95905932A EP95905932A EP0737241B1 EP 0737241 B1 EP0737241 B1 EP 0737241B1 EP 95905932 A EP95905932 A EP 95905932A EP 95905932 A EP95905932 A EP 95905932A EP 0737241 B1 EP0737241 B1 EP 0737241B1
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EP
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Prior art keywords
bleach activator
surfactant
water
particles
bleach
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EP95905932A
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German (de)
English (en)
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EP0737241A1 (fr
Inventor
Benjamin Edgar Chapman
Michael Timothy Creedon
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

Definitions

  • This invention relates to a process for preparing particulate bodies containing lactam bleach activator compounds, particularity caprolactams and valerolactams. Said caprolactam bleach activators are difficult or slow to solubilize and perhydrolyze in cool water (water temperature less than about 35°C).
  • peroxygen bleaches are effective in removing stains and/or soils, as well as visible evidence of stains and/or soils, from textiles and fabrics. Unlike sodium hypochlorite bleaching solution, they can be readily employed in a variety of bleaching and detergent compositions. However, the efficacy of peroxygen bleaches can vary greatly with temperature. These bleaches are only practicable and/or effective when the bleaching solution (bleach and water mixture) is above about 60°C. When employed in a bleach solution at a temperature of about 60°C, or below, peroxygen bleaches are significantly less efficacious than at higher temperatures. Therefore, to obtain a desirable level of bleaching performance at these lower temperatures, extremely high levels of peroxygen bleach must be employed.
  • peroxygen bleaches are most commonly used as detergent adjuvants in home laundry products.
  • the typical textile wash process employing these bleaches utilizes an automatic household washing machine and a wash-water temperature below 60°C.
  • bleach activators or peroxygen bleach activators are generally referred to in the art as bleach activators or peroxygen bleach activators.
  • bleach activators are granular in character and are intended primarily as adjuncts to conventional laundry detergent granules.
  • Such bleach activator granules conventionally comprise a bleach activator in admixture with a coating or carrier material which serves to enhance the stability of the bleach activator and facilitates its uniform dispersion in the granular laundry detergent.
  • acyl lactam bleach activators such as benzoyl caprolactam and benzoyl valerolactam.
  • slow solubilizing lactam bleach activators such as benzoyl caprolactam can be difficult to use in granular laundry detergent compositions because they tend not to solubilize/disperse satisfactorily in the wash water, especially at low wash water temperatures.
  • the unsolubilized bleach activators may fail to be converted to peracids or precipitate on the fabrics in the wash where they then react with the peroxygen bleach and many times spot or remove color from the fabrics.
  • Still another problem in the manufacture of stable, soluble acyl lactam bleach activator particles is the relatively low melting point of some activators.
  • methods for making bleach activator particles involve the use of water to form a mixture of the bleach activator with the other granule additives. After the granule additives and activator have been adequately combined, excess water must be removed, usually by some form of heat-assisted drying. Such drying processes for making acyl lactam bleach activators-containing particles are frequently inefficient because they require temperatures below the melting point ofthe bleach activators to preserve particle form and functionality.
  • a liquid or molten surfactant intimately mixed with the bleach activator would seem to avoid the need for water in the process.
  • the choice of a suitable surfactant is limited.
  • the surfactant should improve solubility of the activator.
  • the surfactant should also allow the final granular product to be solid and non-sticky at room temperature ( ⁇ 20-25°C) and/or while the laundry product, which comprises the activator particle, is in storage where temperatures can reach 50-55°C.
  • the present invention seeks, as one of its objectives, to resolve the problems of utilizing acyl lactam bleach activators in granule form by providing a stable matrix of materials in a particulate form that has satisfactory rate of solution/dispersibility and perhydrolysis characteristics, especially in cool wash water.
  • the invention further seeks to provide a process which does not involve a drying step.
  • the invention seeks to provide bleach activator particles which are suitable for admixing into detergent formulations, i.e., they are non-sticky, have low friability and are free flowing.
  • U.S. Patent 4,290,903, Macgilp, et al., issued September 22, 1981 discloses a process for preparing granular bleach activator products. See also U.S. Patent 4,444,674, Gray, issued April 24, 1984, and U.S. Patent 4,399,049, Gray et al., issued August 16, 1983, and DE 4,024,759, Zeise et al., issued February 6, 1992.
  • a simplified process (I) comprises the steps of: (A) intimately mixing solid acyl lactam bleach activator compounds with a surfactant in liquid or deformable paste form at a temperature below the melting point of the bleach activator compounds; (B) mixing the product of (A) with a crystalline material; and (C) forming the product of (B) into particles.
  • a bleach activator-stable, water-soluble binder may be added in either step (A) or step (B).
  • the invention encompasses a non-aqueous process fbr preparing bleach activator particles, again without a heat-assisted drying process, comprising forming a co-melt of a substantially dry surfactant (typically, less than about 10%, preferably less than about 1%, by weight of water) and a caprolactam or valerolactam bleach activator, solidifying said co-melt by cooling, and forming the resulting solidified co-melt into particles, e.g., by grinding, flaking, extruding, cutting or other convenient means.
  • a substantially dry surfactant typically, less than about 10%, preferably less than about 1%, by weight of water
  • a caprolactam or valerolactam bleach activator solidifying said co-melt by cooling, and forming the resulting solidified co-melt into particles, e.g., by grinding, flaking, extruding, cutting or other convenient means.
  • homogeneous melts comprising the lactam bleach activators and one or more of the preferred surfactants herein can be prepared at surfactant:lactam weight ratios of 10:1 to 1:10, solidified by chilling and formed into particles.
  • co-melt herein is meant that the acyl lactam bleach activator is heated to a temperature above its melting point, and the surfactant is added to that melt and intimately admixed. At that temperature, the surfactant may or may not have reached its melting temperature.
  • the temperature is not allowed to reach the decomposition temperature of either the lactam or the surfactant.
  • the particles formed from the co-melt may be agglomerated, typically by means of a binder, as in processes I or II, above.
  • the present invention concerns a process (I), preferably continuous, for preparing particulate bodies containing one or more acyl lactam bleach activator compounds.
  • Said activators can be difficult or slow to solubilize in cool water (below about 35°C).
  • Said process does not include a heat-assisted drying step.
  • Said process comprises the steps of: (A) intimately mixing solid acyl lactam bleach activator compounds with a composition in deformable paste form comprising one or more surfactants and water (approximately in a 1:1 ratio); (B) mixing the product of (A) with a crystalline, bleach activator-compatible material; and (C) forming the product of (B) into particles.
  • a bleach activator-stable, water-soluble binder may be added in either step (A) or step (B).
  • deformable paste is meant a mobile pasty mass whose shape can be altered or changed by exerting a shear force to the mass (usually by hand pressure) and has a consistency similar to solid Crisco® or PlaydoughT.
  • Step (B) preferably includes mixing the product of step (A) with a crystalline, bleach activator-compatible, hydratable material at a temperature which is between 0°C and the temperature of hydration of the hydratable material, until the product of (B) comprises less than 15 wt. %, preferably less than 10 wt. %, more preferably less than about 8 wt. %, of non-hydrated water.
  • the hydratable, crystalline material acts to reduce the non-hydrated water level in the mixing step to the desired level for good particle formation and to act as a filler to achieve a desirable bleach activator concentration in the product.
  • temperature of hydration is meant the temperature that the crystalline material will release hydrated or bound water.
  • non-hydrated water sometimes called “free water” is meant water in the product but which is not bound with the crystalline, bleach activator-compatible, hydratable material.
  • the level of non-hydrated water in the product of step (B) can be determined by air drying the product sample at a temperature below the temperature of hydration of the crystalline material.
  • the amount of non-hydrated water in the sample can be calculated from the difference in the weight of the sample before and after air drying.
  • steps inserted between the steps of this invention e.g., additional mixing and/or extruding.
  • the intimate mixture step (A) takes place in a high shear mixer, an extruder, or an extruder/mixer, most preferably in an extruder/mixer.
  • step (B) the step in which the bleach activator/surfactant, binder, and crystalline, bleach activator-compatible material are mixed, step (B), takes place in a low or a high speed mixer.
  • a low or a high speed mixer examples include: V-blender with intensifier bar, pin mixers and /or plough share mixers. Most preferred is a pin mixer.
  • step (B) takes place in a high speed mixer, like a Lodige CB.
  • the particle formation step (C) is accomplished by forming a granulate in a Turbolizer or a Lodige KM agglomerator or forming an extrudate in an axial or radial extruder, most preferably in a Fuji Paudal, axial or radial extruder.
  • step (B) takes place in a low speed mixer, such as a Lodige KM
  • step (C) takes place in other low speed mixer/agglomerators, known in the art.
  • Particle forming in the Lodige KM can be accomplished by extended mixing in the same unit utilized for step (B), i.e., until the mixture, preferably, has less than about 10 wt. % of non-hydrated water and acceptable particles size is obtained. Because of the intimate surfactant mixing step, these particles have a good rate of solubility in the wash water.
  • a third optional ingredient for inclusion in step (B) mixing is process recycle (finished product return), which serves to improve process control.
  • the present invention concerns yet another process (II), for preparing particulate bodies containing one or more acyl lactam bleach activator compounds.
  • Said process comprises the steps of (A) intimately mixing molten acyl lactam bleach activator compounds with one or more surfactants, which may or may not be molten themselves in this operation.
  • bleach activator-stable, water-soluble binder materials may be added to the molten mixture at this point.
  • step (B) the molten intimate mixture of acyl lactam, surfactant and optional binder material is cooled to a solidified mass.
  • the cooling/solidified mass is formed into particulate matter suitable for admixing into detergent formulatlions by processes such as (but not limited to) grinding, flaking, agglomerating, extruding, sieving.
  • the cooled intimate mixture of acyl lactam and surfactant is ground into a fine powder, and a final particulate suitable for admixing into detergent formulations is prepared by agglomerating said ground fine powder utilizing a hot melted water soluble binder in an agglomeration process.
  • agglomeration process is as described in the foregoing section, process (L) above.
  • an object of this invention is to provide a method of manufacture which does not involve the need for heat assisted drying. This, is important due to the low melting point sensitivity of the useful acyl lactam bleach activators described herein.
  • Use of high temperatures desirable for efficient drying can cause melting and particle stickiness or even particle deformation/destruction and must be avoided.
  • use of low temperatures for drying are quite inefficient.
  • Use of the processes of the present invention obviate the need for heat assisted drying entirely. Certain of the processes are nonaqueous, and thus require no drying. However, certain of the processes described herein allow the use of signficant amounts of water (especially in surfactant pastes), which can also be handled without drying by utilizing the present techniques and teachings.
  • the processes of the present invention contain from 10 to 90, preferably from 40 to 80, most preferably from 50 to 80, weight % of solid acyl lactam bleach activators.
  • the preferred ratio of bleach activator to surfactant in the intimate mixing step (A) is between 100:1 and 4:1, more preferably between 50:1 and 5:1, most preferably between 10:1 and 7:1.
  • the preferred acyl lactam bleach activators are solids at temperatures of about 70°C and below.
  • Suitable caprolactam bleach activators are of the formula: wherein R 6 is phenyl or a substituted phenyl group.
  • substituted benzoyl caprolactams include 4-chlorobenzoyl caprolactam, 4-nitrobenzoyl caprolactam, 2-methylbenzoyl caprolactam, 2,4-dichlorobenzoyl caprolactam, pentafluorobenzoyl caprolactam, and mixtures thereof.
  • Suitable valerolactam bleach activators are of the formula: wherein R 6 is phenyl or a substituted phenyl group.
  • lactams are well known in the art. Examples I and II, included below, illustrate preferred laboratory syntheses. Examples of substituted benzoyl valerolactams include 4-chlorobenzoyl valerolactam, 4-nitrobenzoyl valerolactam, 2-methylbenzoyl valerolactam, 2,4-dichlorobenzoyl valerolactam pentafluorobenzoyl caprolactam, and mixtures thereof.
  • caprolactam bleach activators are preferably not absorbed onto the peroxygen bleaching compound. To do so in the presence of other organic detersive ingredients could cause premature perhydrolysis, loss of activity and even safety problems.
  • bleach activator can be added to the bleach activator before incorporation into the final product.
  • buffers and chelants can optionally be included.
  • Detergent compositions and bleaching compositions containing lactam bleach activators provide extremely effective and efficient surface bleaching of textiles. Stains and/or soils are removed from the textiles.
  • washing solutions wherein the pH of such solution is between about 8.5 and 10.5 in order to facilitate the perhydrolysis reaction.
  • pH is normally obtained with substances commonly added to detergent compositions, such as builders and alkaline materials, which are optional components of the bleaching systems herein.
  • Such systems are useful not only for fabric laundering, but also in automatic dishwashing compositions.
  • the particulate bodies of this invention also include bleach activator-stable, water-soluble detergent surfactants selected from the group consisting of anionics, nonionics, zwitterionics, ampholytics, and mixtures thereof.
  • the preferred ratio of bleach activator to surfactant in the intimate mixing step is between 100:1 and 4:1, more preferably from between 50:1 to 5:1, most preferably from between 10:1 to 7:1.
  • Anionic surfactant is preferred and salts of C 11-13 linear alkyl benzene sulfonate, C 12-16 alkyl sulfate and/or C 12 -C 18 methyl ester sulfonates are more preferred.
  • Sodium C 11-13 linear alkyl benzene sulfonate is most preferred.
  • the surfactant in process modes I and II herein is liquid at temperatures below the melting point of the solid bleach activators, about 70°C and below, or a deformable paste comprising surfactant and water (approximately 1:1 ratio of surfactant to water).
  • Nonlimiting examples of surfactants useful herein include the conventional C 10 -C 20 soaps; C 11 -C 16 alkyl benzene sulfonates; the C 12 -C 18 primary and secondary alkyl sulfates and C 12 -C 18 unsaturated (alkenyl) sulfates such as oleyl sulfate; the branched-chain C 10 -C 18 alkyl sulfates; the C 10 -C 18 alkyl ethoxy sulfates; the C 10 -C 18 alkyl polyglycosides and their corresponding sulfated polyglycosides; the C 10 -C 18 polyhydroxy fatty acid amides, especially the C 10 -C 18 fatty acid amides of N-methyl through N-hexyl glucamine, see WO 9,206,154 and 9,206,984; C 12 -C 18 alkyl methyl ester sulfonates (a-sulfonated
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C 11-13 LAS.
  • anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • Water-soluble nonionic surfactants are also useful in the compositions of the invention.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature.
  • the length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from 6 to 15 carbon atoms, in either a straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 8 moles of ethylene oxide per mole of alcohol.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Suitable "hard” nonionic surfactants that can be utilized as both surfactant and binder materials are polyethylene glycols, polyethylene oxide condensates of alkyl moieties, and polyethylene oxide condensates of alkyl phenols.
  • Suitable polyethylene glycols are homopolymers of ethylene oxide having the general formula HO(C 2 H 4 O) n H, having an average molecular weight of from 2,000 to 15,000, preferably from 3,000 to 10,000.
  • Suitable polyethylene oxide condensates of alkyl moieties are of the formula R-(C 2 H 4 O) n H, wherein R is C 10 -C 18 and n is 20-100.
  • Suitable condensation products of alkyl phenols have an alkyl group containing from 6 to 12 carbon atoms, in either a straight or branched chain configuration, with ethylene oxide.
  • Such "hard” surfactants provide good solubility, which improves the rate of perhydrolysis of the bleach activator, and also provide suitable binding of the particles.
  • the bleach activator particles of this invention optionally, but preferably, comprise bleach activator-stable, water-soluble binders.
  • the materials that can be utilized as binders are polyethylene glycols, fatty acids, film-forming polymers, certain "hard” nonionic surfactants, and mixtures of these materials. Such binders should not be reactive with the bleach activators of the present invention. If the particles are placed in a detergent composition, the binder should not be reactive with the components of the detergent composition. Ideal binder materials have a low hygroscopicity upon storage but should be soluble or dispersible in water. This allows for dispersion and release of the bleach activator in the bleach or wash solution. It is also essential that the employed binder materials do not melt below 50°C-55°C to avoid storage stability problems. Any melting of the binder during warm storage results in the particles becoming sticky and non-handleable.
  • the binder can be mixed with the bleach activator and surfactant during the early mixing stage step (A) or in a second step (B).
  • the binder can be added as a hot melt or in an aqueous mixture.
  • the binder can be dry added and mixed with the bleach activator or mixed with water before adding to the surfactant/bleach activator mixture.
  • Suitable "hard” nonionic surfactants that can be utilized as both surfactant and binder materials are polyethylene glycols, polyethylene oxide condensates of alkyl moieties, and polyethylene oxide condensates of alkyl phenols.
  • Suitable film-forming polymers useful as binder materials in the particles of the present invention are the polymers derived from the monomers such as vinyl chloride, vinyl alcohol furan, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, styerene, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamide, ethylene, propylene and 3-butenoic acid.
  • Preferred polymers of the above group are the homopolymers and copolymers of acrylic acid, hydroxyacrylic acid, or methacrylic acid, which in the case of the copolymers contain at least 50%, and preferably at least 80%, by weight, units derived from the acid.
  • the particularly preferred polymer is sodium polyacrylate.
  • Other specific prefered polymers are the homopolymers and copolymers of maleic anhydride, especially the copolymers with ethylene, styrene and vinyl methyl ether.
  • film-forming polymers useful as binder materials include the cellulose esters such as carboxy methyl cellulose, hydroxyethyl cellulose, methyl cellulose, and hydroxypropyl cellulose.
  • binder materials examples include sorbitan fatty acid esters selected from the group consisting of sorbitan monolaurate, dilaurate, trilaurate, monopalmitate, monostearate, distearate, tristearate, monooleate, dioleate, and trioleate, are preferred. Ethoxylated varieties of these compounds are also useful. For example, sorbitan esters having an average total level of ethoxylation of from 4 to 100, and preferably 20 to 85 moles of ethylene oxide per mole of sorbitan, are preferred. Also preferred binder materials include sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate.
  • Polyethylene glycols having an average molecular weight of from 4,000 to 8,000 are most preferred, as is a C 12 -C 14 ethoxylate having about 50 moles ethylene oxide per alkyl group.
  • the level of binder material useful within the particles within the invention is from 5% to 25 wt. % of the body, more preferably from 10% to 25 wt.%.
  • the particles of the present invention may also contain all of the usual components of detergent compositions so long as they are inert with respect to the bleach activator, surfactant, and binder material.
  • Such components include other peroxygen bleach activators, color speckles, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil-suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
  • the purpose ofthe crystalline, bleach activator-compatible material is to dilute the non-hydrated water level in the mixing step (step B) to a desired level for good particle formation, and to act as filler to achieve a desirable bleach activator concentration in the product.
  • This material can be divided into hydratable and non-hydratable materials. It is preferably not film-forming material.
  • Suitable non-hydratable materials include alumino-silicates and/or crystalline surfactants.
  • Suitable hydratable materials preferably have a pH between 5.0-8.0, most preferably between 6.0-7.0. These are preferably selected from the group consisting of sodium sodium acetate, sodium phosphate, sodium tripolyphosphate, sodium acid phosphite, lithium formate, lithium sulfate, zinc nitrate, and combinations thereof.
  • sodium sulfate (most preferred).
  • Materials to be avoided are halides and compounds containing heavy metals such as iron.
  • the bleach activator-particles herein preferably comprise from 10 to 95 weight % crystalline material.
  • the bleach activator particles made by the present invention can be used by themselves as a laundry bleach additive, but are preferably included in a conventional granular laundry detergent composition.
  • Preferred particulate bleaching compositions made according to this invention comprise:
  • More preferred particulate bleaching compositions made according to this process comprise:
  • the lactam bleach activator is combined with a surface active agent, to aid in its solubility and improve the rate of perhydrolysis, through the use of an intimate mixing device. Without this step dissolution rates of the bleach activator particles have been found to be hindered, thus hurting overall performance in a washing environment.
  • the preferred ratio of bleach activator to surfactant is 10:1.
  • the preferred surfactant is selected from the group consisting of C 11-13 linear alkyl benzene sulfonate, C 12-16 alkyl sulfate, C 12 -C 18 methyl ester sulfonates, or mixtures thereof.
  • the preferred intimate mixing device is a Teledyne-Readco Processor (extruder/mixer).
  • the Teledyne-Readco Processor is an intimate blending device (an extruder/mixer) with low residence time capabilities (less than about 30 seconds) but is capable of handling high viscosity, low water solids. It is preferably employed in the process to break down the bleach activator into small crystals, which has been found herein to maximize solubility, especially in cool water (less than about 35°C). Secondly, and importantly, the bleach activator is intimately mixed in the extruder/mixer with preferred surfactant. This step coats much of the bleach activator crystal surface area to aid in the ultimate dispersibility and solubility of relatively insoluble bleach activators.
  • the output of this intimate mixer is a highly viscous paste (similar to Crisco® or PlaydoughT). In processes which involve the addition of water, the free water content in the viscous paste is less than about 15%. (All of the water is "Free", non-hydrated).
  • the Readco is an axial, twin barrel processing device having various adjustable internal paddles.
  • these paddles may be configured in a number of ways to accomplish appropriate intimate mixing. Most useful combinations are double flat paddles in series, interspersed with helical paddles to force the bleach activator/surfactant paste mixture through the unit.
  • Surfactant and bleach activator are pumped and metered into the extruder/mixer, simultaneously, or alternatively, the surfactant may be added sequentially about half way down its barrel.
  • a binder may be added to either stream.
  • the surfactant and bleach activator are fed at temperatures below the melting point of the bleach activator.
  • the ratio of bleach activator to surfactant is typically 10:1 on an active basis.
  • the surfactant/water mixture is approximately 50% active and has a deformable/mobile paste-like consistency.
  • the output of the Readco is a viscous paste which comprises approximately 9% water and which is ⁇ 75% active.
  • a binder may be mixed with the bleach activator and surfactant in the above stage or in a second mixing stage.
  • the preferred method is to use a Lodige CB continuous mixer, which is preferably used to prepare a mixture of the product of step (A), binder, crystalline material (in processes which comprise the addition of surfactant/water deformable paste) and, optionally, process recycle for particle formation.
  • the purpose of the mixer is three-fold: (1) provide an opportunity to reduce the free water of the step (A) paste to a level which is acceptable for particle formation (in the process which incorporates water in step (A)); (2) homogenize the paste, binder, crystalline material, and optional recycle components so that a homogeneous particle can be formed; and (3) offer sufficient residence time for a portion of the non-hydrated water in the mixture, if present, to become hydrated by the hydratable, crystalline material.
  • the streams entering the mixer are at a temperature below the melting point of the bleach activator.
  • Residence time in the mixer is critical in achieving the desired level of hydration while ensuring the mixer does not overmix and form oversized agglomerates.
  • the formation of what amounts to a homogeneous damp powder is preferred.
  • the contents in the mixer should never reach or exceed the melting point of the bleach activator or of the hydration temperature for the crystalline material. To accomplish all these aspects of this mixing stage, both rotation speed and fill level should be properly controlled.
  • the "damp" powder discharge must have a free water level less than about 15% (most desired less than about 8%) for proper extrusion characteristics (preferred particle forming process - see step (C) below).
  • the mixture should be cooled to below the melting point of the binder. The cooled material can then be flaked and/or ground to the desired size (approximately 200-800 micron average).
  • the cooled bleach activator/surfactant/binder mixture can be extruded and cooled, or agglomerated in a plough share mixer, such as a Lodige KM (preferred particle forming process - see step (C) below).
  • the resulting product from step (B) should have less than about 15% water depending on the choice of aqueous or non-aqueous step (A) employed and on the particle formation equipment used.
  • the preferred methods are to use either an agglomeration or extrusion process.
  • a plough share mixer is used, such as a Lodige KM.
  • extrusion processes a Fuji-Paudal continuous extruder, which forms the product produced in step (B) into cylinders of approximately 1 mm in diameter (hole diameter of die plate), is preferred.
  • the purpose of the extruder is to form the bleach activator mixture into defined particles which can be handled, shipped and finally blended into a detergent.
  • Finished particles should exhibit acceptable physical characteristics such as attrition resistance, low surface area per unit volume for stability optimization, acceptable rate of solubility, good perhydrolysis, aesthetically appealing color and acceptable flow characteristics, i.e., non-sticky and free flowing, and with sufficient structural integrity for formulation purposes.
  • a COMIL basket type grinder is preferably used to size reduce agglomerated or extruded "overs" from the sizing operation.
  • the output is blended with the "fines” and are returned as process recycle. They will enter the process at step (A) or (B).
  • the "Save” component of the sizing operation can undergo a coating operation targeted at improving the flowability of the final particles. This is often desired to ensure bleach activator agglomerates or extrudates can be bulk stored, shipped and unloaded with ease.
  • the coating can be a typical "free-flow" aid dry coating such as a silica powder or fine zeolite powder that can be applied in a typical mix drum.
  • reaction mixture is then cooled, filtered, and the solvent removed by rotary evaporation to yield 121.7 g of the product as an oil which crystallizes on standing.
  • This crude product is then redissolved in toluene and precipitated with hexane, yielding 103 g (79% theoretical yield) of a white solid which is shown by NMR to be over 95% pure, with the remaining material being benzoic acid.
  • Benzoyl caprolactam is synthesized and recovered according to the procedure in Example #1.
  • Sample 3A Approximately 162.5 grams of benzoyl caprolactam is combined with 5 grams dry C 12 AS surfactant and 35 grams of 50% active NaC 11-13 alkyl benzene sulfate (LAS) surfactant (in deformable paste form) at about 120°F (49°C). This combination is intimately mixed with pressure by hand mixing in a laboratory mortar and pestle into a creamy paste and is allowed to cool to ambient temperature (approximately 25°C). Thus, the ratio of acyl lactam to dry active surfactant is 162.5:22.5, or about 7:1. The amount of water in this intimate mixture is about 17.5:202.5, or about 8.6%.
  • LAS active NaC 11-13 alkyl benzene sulfate
  • This mixture is placed into a small Braun Food Processor, Multiprac 280, along with 47.5 g. anhydrous Sodium Sulfate and mixed at medium speed for about 20 seconds to cause mixing of the dry sodium sulfate into the lactam/surfactant paste and eventual agglomeration and particle formation.
  • the sodium sulfate acts as a hydrating agent, and hydrates a substantial amount of the free water in a short time.
  • the amount of active bleach activator (benzoyl caprolactam) in this final mixture is 162.5 g. out of 250 g., or 65%.
  • a dry mixture of benzoyl caprolactam, dry C 12 AS and dry sodium sulfate are added to the Braun Food Processor and mixed.
  • the warm, 50% active NaC 11-13 alkyl benzene sulfate (LAS) deformable paste is quickly added and all ingredients mixed as in sample 3A.
  • Mixing, agglomeration and particle formation occurs as in sample 3A.
  • the sodium sulfate acts as a hydrating agent, and hydrates a substantial amount ofthe free water in a short time.
  • the amount of active bleach activator (benzoyl caprolactam) in this final mixture is 162.5 g. out of 250 g., or 65%.
  • the granulations thus formed are sieved using multiple screen sizes to retain particles sized between 212-710 microns using a laboratory RoTap sieve shaker.
  • the resulting particles are suitable for admixing into granular detergent formulations, and when subjected to a source of oxygen at a pH of about 10.5, perhydrolyze to form the peracid, perbenzoic acid, which is a useful bleaching agent in cool water, especially in handwashing situations.
  • Sample 3C - A third sample is prepared, wherein a simple dry mixture of benzoyl caprolactam and sodium sulfate is made in the Braun Food Processor and wherein the benzoyl caprolactam comprises 65% of the total weight. No surfactant is added to Sample 3C..
  • the three samples are tested for perhydroylsis rate using a standard testing method wherein a model detergent system comprising LAS, builders and sodium perborate are delivered to form an aqueous wash solution at a pH of about 10.5 and temperature of about 73°F (23°C).
  • the percent of theoretical available oxygen (AvO) is measured versus time after the acyl lactam is added to the simulated wash solution. Table below shows the results, indicating significant improvement for the sample wherein the surfactant (LAS) is intimately mixed with the relatively hydrophobic benzoyl lactam.
  • This method measures available oxygen (AvO) in detergent solutions, allowing determination of perhydrolysis rate of bleach activators.
  • Potassium iodide reacts with the peroxide present to form free iodine which is titrated with sodium thiosulfate.
  • the analysis is performed with a METTLER DL-25 autotitrator.
  • Other equipment required includes two and four place laboratory balances, magnetic stirrers, timer, general glassware, sampling syringes and an ice bath.
  • the method has the ability to analyze both peracid AvO and total AvO. This is accomplished by the use of the enzyme catalase which destroys peroxide in solution, leaving only peracid for AvO measurement.
  • a model detergent is used, which contains LAS, builders and sodium perborate (oxygen source).
  • SAMPLE CONDITIONS (For Benzoyl Caprolactam ) A) Test Temperature 25°C / 77°F ( ⁇ 2° C or ⁇ 3° F)
  • Typical acyl lactam concentration is between 60-200 ppm.
  • Benzoyl caprolactam is synthesized and recovered according to the procedure in Example #1.
  • Non-aqueous pre-mix process (Samples A,B,C,D,F,G)
  • Dry, particulate mixtures comprised of benzoyl caprolactam, dry surfactants, organic binders, and processing aids are mixed together in beakers. Sample size is about 100 grams.
  • the dry blends are ground in a Braun coffee bean grinder for about one minute to give smaller particle size for more complete and intimate mixing.
  • aqueous mixture comprised of benzoyl caprolactam particles, aqueous surfactant paste, organic binder, and processing agents are mixed together in beakers. Sample size is about 100 grams. It is thoroughly mixed with a spatula to make a uniform paste.
  • the mixtures are then extruded under force through a die plate comprised of a one millimeter opening.
  • the extruder is heated to approximately 120°F-135°F (49°C-57°C) depending on the melting temperature of the binder, and mixture materials.
  • the temperature of the mixtures and processing equipment is always lower than the melting point of the bleach activator.
  • the extrudates formed by this process are sized into lengths of 2 to 5 millimeters, preferably 1 to 2 millimeters.
  • the extrudates can also ground into particles and sized through a sieve with 850 micron openings.
  • Typical formulations for the above described mixtures are as follows: TYPICAL FORMULATIONS - PARTS BASIS (W/W) INGREDIENT FUNCTIONALITY A B C D E F G Benzoyl Caprolactam A 80 75 75 75 75 75 75 75 C12 Alkyl Sulfate S 7 9 12 7 0 7 7 (dry particles) C12 Alkyl Sulfate S 0 0 0 0 25 0 0 (aqueous paste 28% conc.) Palmitic Acid P 5 7 0 6 5 5 5 5 5 5 5 Polyethelene glycol B 8 9 13 7 8 8 7 (molecular wt.
  • Tergitol 15-S-30 is a C 11 -C 15 linear, secondary alcohol reacted with ethylene oxide with 30 moles of ethylene oxide per mole of alcohol made by Union Carbide.
  • Sokalan CP-5 is a polyacrylate binder made by Hoechst.
  • Neodol 45-13 is C 14 -C 15 alkyl ethoxylate with 13 moles of ethylene oxide per molecule alkyl group made by Shell Chemicals.
  • Benzoyl caprolactam is synthesized and recovered according to the procedure in Example #1.
  • a dry mixture of Benzoyl caprolactam, 7.3 kg; a binder, Carboxy Methyl Cellulose (CMC), 400 g.; and sodium sulfate (500 g.) is prepared.
  • a wet surfactant mixture is prepared comprising NaC 11-13 alkyl benzene sulfate (LAS), 600 g. of 50% active paste; C 12 alkyl sulfate (C 12 AS), 1.2 kg dry powder; and water, 1925 g., and this second mixture heated to 120°F.(49°C)
  • a die plate comprised of circular holes having a diameter of 0,95 mm (3/8 inch) cause moist, similarly sized extrudates (or noodles) to be formed which are collected.
  • the amount of acyl lactam in the wet noodles is about 75% and the total amount of water in this intimate mixture is about 9.2%.
  • Noodles are collected during the course of the run, which is about 30 minutes, during which time samples are collected.
  • Sample 5A A sample of the moist noodles is gently dried at about 100°F (38°C) and hand granulated.
  • Sample 5B A sample of the moist noodles is added to a Braun Food Processor, Multiprac 280, and particles are formed by agglomeration at medium speed with addition a 100:1 wt/wt ratio of sodium sulfate: sodium alumino-silicate, such that the final particulate product contains about 50% active acyl caprolactam and total water content is about 6%.
  • samples having identical compositions to sample 5B are made with the total amount of sodium sulfate (and silicate, if desired) incorporated into the dry mixture feed to the Teledyne-Readco extruder mixer, described above, and a dry, formed extrudate is made with excellent properties.
  • the binder material may be added to the wet surfactant mixture, if desired, without deviating from the scope of the invention.
  • Neodol 45-7 Shell Chemical Co. nonionic surfactant containing alkyl group of 14-15 carbon atoms and ethoxylated with 7 moles EO
  • This combination is intimately mixed (as in Example #3A) with pressure by hand mixing in a laboratory mortar and pestle into a doughy paste and allowed to cool to ambient temperature. This is a non-aqueous mixture.
  • This mixture is placed into a small Braun Food Processor, Multiprac 280, along with 15 grams anhydrous sodium sulfate and 30 grams sodium alumino silicate and mixed at medium speed for about 20 seconds (as in Example 3A) to cause mixing of the two crystalline materials into the lactam/surfactant/binder paste and eventual agglomeration and particle formation.
  • the crystalline materials act as diluents and particle formation centers.
  • samples 5A and 5B and 5C are sieved, sized as in Example #3. All resulting particles are suitable for admixing into granular detergent formulations and when subjected to a source of oxygen at a pH of about 10.5, perhydrolyze to form the peracid, perbenzoic acid, which is a useful bleaching agent in cool water, especially in handwashing situations.
  • the preferred particles prepared in the herein-described manner have a size in the range of from about 200 micrometers to about 1200 micrometers.
  • the agglomerates are useful in laundry, bleach and automatic dishwashing compositions to augment the bleaching action of the so-called "per-bleaches" such as sodium perborate, sodium percarbonate, potassium persulfate, and the like.
  • the molten mass is transferred to separate 8"x12" glass Pyrex dishes, so that the thickness of the resulting molten material is approximately 2-5 mm.
  • the dishes are then placed into a constant temperature room at 120°F (49°C) overnight.
  • each sample dish is returned to ambient temperature conditions in the laboratory and allowed to cool further for approximately 1-3 hours.
  • the cooled, solidified mass for each sample is removed by hand utilizing a stainless steel spatula. Removal is accomplished by "chipping out" irregularly shaped solidified chunks of material, most of which range in size from about 0.5 cm to about 5 cm.
  • This solidified material is then ground into granular form using a Braun coffee bean grinder, or similar size reduction device.
  • the particles are then screened using a Tyler 20 mesh screen (850 micron opening) and the particles passing through the screen opening are collected.
  • An intimate mixture of benzoyl caprolactam and C 12 alkyl sulfate is prepared as follows: 150 parts (by weight) of benzoyl caprolactam is melted to a temperature between 175°F and 200°F (79°C to 93°C). To this, 16 parts (by weight) of C 12 alkyl sulfate powder (90-95% active) is added and again intimately mixed for 1-3 minutes using a laboratory high shear tissue homogenizer (Janke and Kunkel Model SDT, with a small mixing head).
  • the molten mass is transferred to 8"x12" glass Pyrex dishes, so that the thickness of the resulting molten material is 2-5 mm.
  • the dishes and molten material are allowed to cool at ambient laboratory conditions to stabilize at about 70°F-75°F (21°C-24°C).
  • the solidified mass is removed by hand utilizing a stainless steel spatula. Removal is accomplished by "chipping out” irregularly shaped solidified chunks of material, most of which range in size from about 0.5 cm to about 5 cm.
  • This solidified material is then ground into granular form using a Braun coffee bean grinder, or similar size reduction device.
  • the particles are then screened using a Tyler 20 mesh screen (850 micron opening) and the particles passing through the screen opening are collected. These are identified as "accepts”.
  • molten binder 20 grams is slowly added to the above particles (about 10 minutes). This operation is conducted while the mixer with the flat beater blade attachment is running at a slow to moderate speed.
  • the molten binder (a tallow alcohol ethoxylated to 25 moles ethylene oxide to one mole of alcohol) is added by warm transfer pipette in dropwise fashion.
  • Agglomerates of the benzoyl caprolactam/C 12 AS particle and binder are formed as the binder cools from the molten to solid state. These agglomerates are sized by screen, and the portion passing through a Tyler 14 mesh screen (1180 micron opening), but retained on a Tyler 65 screen (212 micron opening) are collected.
  • the collected agglomerates are tested for Available Oxygen according to the Method for AvO Analysis described in Example VI(A). Results of this testing show that the particles display 67.5% Theoretical Available Oxygen (AvO) at 10 minutes time.

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Claims (12)

  1. Procédé pour préparer des corps particulaires contenant un ou plusieurs composés activateurs de blanchiment de type acyl-lactame, caractérisé par les étapes consistant à (A) mélanger intimement les composés activateurs de blanchiment de type acyl-lactame solides avec un ou plusieurs tensioactifs sous forme liquide ou sous la forme d'une pâte déformable à une température inférieure au point de fusion des composés activateurs de blanchiment ; (B) mélanger le produit de l'étape (A) avec un matériau cristallin pour obtenir une poudre humide ; et (C) mettre le produit obtenu précédemment sous la forme de particules.
  2. Procédé selon la revendication 1, dans lequel ledit activateur de blanchiment est choisi dans l'ensemble constitué par les benzoyl-caprolactames substitués, le benzoyl-caprolactame, les benzoyl-valérolactames substitués, le benzoyl-valérolactame, et leurs mélanges.
  3. Procédé selon la revendication 1, dans lequel l'étape (A) comprend en outre le mélange d'un liant soluble dans l'eau avec l'activateur de blanchiment et le tensioactif.
  4. Procédé selon la revendication 1, dans lequel l'étape (B) comprend en outre le mélange de la composition d'activateur de blanchiment/tensioactif de l'étape (A) avec un liant soluble dans l'eau.
  5. Procédé selon la revendication 1, dans lequel le matériau cristallin est un silicate ou un tensioactif cristallin.
  6. Procédé selon la revendication 1, dans lequel l'étape (B) comprend le mélange du produit de l'étape (A) avec un matériau hydratable cristallin à une température qui est située dans la plage allant de 0°C à la température d'hydratation du matériau hydratable, jusqu'à ce que le produit de (B) comprenne moins de 15 % en poids d'eau qui n'est pas de l'eau d'hydratation.
  7. Procédé selon la revendication 6, dans lequel le matériau cristallin est choisi dans l'ensemble constitué par le sulfate de sodium, l'acétate de sodium, le phosphate de sodium, les tripolyphosphates de sodium, le phosphite acide de sodium, le formiate de lithium, le sulfate de lithium, le nitrate de zinc, et leurs combinaisons.
  8. Procédé selon la revendication 1, dans lequel le tensioactif est choisi dans l'ensemble constitué par les tensioactifs anioniques et non-ioniques, et leurs mélanges, de préférence dans lequel le tensioactif est choisi dans l'ensemble constitué par les (alkyl linéaire)benzènesulfonates de sodium, les alkylsulfates en C12 à C16, les méthylestersulfonates en C12 à C18, les alcools éthoxylés et leurs mélanges.
  9. Composition d'activateur de blanchiment particulaire préparée conformément à la revendication 1, caractérisée en ce qu'elle comprend :
    (1) de 10 à 90 % en poids d'un ou de plusieurs activateurs de blanchiment de type acyl-lactame solides ;
    (2) de 1 à 40 % en poids d'un tensioactif choisi dans l'ensemble constitué par les tensioactifs anioniques, non-ioniques, zwittérioniques, ampholytes, et leurs mélanges ; et
    (3) de 5 à 25 % en poids d'un liant choisi dans l'ensemble constitué par les polyéthylèneglycols, les acides gras, les polymères filmogènes, les produits de condensation oxyéthylénés de groupements alkyle, les produits de condensation polyoxyéthylénés d'alkylphénols, et leurs mélanges.
  10. Procédé non aqueux pour préparer des particules d'activateur de blanchiment, qui consiste à former une masse fondue conjointe d'un tensioactif pratiquement anhydre et d'un activateur de blanchiment de type caprolactame solide ou de type valérolactame solide à une température supérieure au point de fusion dudit activateur, à solidifier ladite masse fondue conjointe, et à mettre la masse fondue conjointe solidifiée résultante sous la forme de particules.
  11. Procédé selon la revendication 10, dans lequel lesdites particules sont agglomérées au moyen d'un liant.
  12. Composition particulaire pour le lavage du linge, le blanchiment ou le lavage automatique de la vaisselle, caractérisée en ce qu'elle comprend d'environ 0,5 à environ 40 % en poids des particules produites par le procédé de la revendication 1 ou de la revendication 11.
EP95905932A 1993-12-23 1994-12-13 Procede de fabrication d'un activateur de blanchiment au lactame contenant des particules Expired - Lifetime EP0737241B1 (fr)

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US17330893A 1993-12-23 1993-12-23
US173308 1993-12-23
US08/350,089 US5534196A (en) 1993-12-23 1994-11-29 Process for making lactam bleach activator containing particles
US350089 1994-11-29
PCT/US1994/014361 WO1995017498A1 (fr) 1993-12-23 1994-12-13 Procede de fabrication d'un activateur de blanchiment au lactame contenant des particules

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EP0737241B1 true EP0737241B1 (fr) 1999-05-26

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Families Citing this family (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5686015A (en) * 1994-08-31 1997-11-11 The Procter & Gamble Company Quaternary substituted bleach activators
BR9509731A (pt) * 1994-11-18 1997-09-30 Procter & Gamble Composições de alvejamento e aditivos de alvejante compreendendo ativadores de alvejante eficazes em baixas concentrações de perhidroxila
DE19518039A1 (de) * 1995-05-17 1996-11-21 Basf Ag Verwendung von heterocyclischen Verbindungen als Aktivatoren für anorganische Perverbindungen
GB9519094D0 (en) * 1995-09-19 1995-11-22 Warwick Int Group Granulated active with controlled release
CZ229598A3 (cs) * 1996-01-29 1999-01-13 The Procter & Gamble Company Způsob přípravy částicové složky bělicího aktivátoru
JP3164826B2 (ja) * 1996-03-08 2001-05-14 ザ、プロクター、エンド、ギャンブル、カンパニー 混練／押出法による改善された溶解度を有する第二級アルキルサルフェート界面活性剤
DE19609953A1 (de) * 1996-03-14 1997-09-18 Basf Ag Feste Zusammensetzung aus heterocyclischen Verbindungen und/oder Oximestern und inerten porösen Trägermaterialien und ihre Verwendung als stabile Bleichaktivator-Komponente in Wasch-, Bleich- und Reinigungsmitteln
GB9613899D0 (en) * 1996-07-03 1996-09-04 Procter & Gamble Cleansing compositions
DE19641708A1 (de) * 1996-10-10 1998-04-16 Clariant Gmbh Verfahren zur Herstellung eines gecoateten Bleichaktivatorgranulats
DE19649375A1 (de) 1996-11-29 1998-06-04 Henkel Kgaa Acetonitril-Derivate als Bleichaktivatoren in Reinigungsmitteln
DE19704634A1 (de) 1997-02-07 1998-08-27 Henkel Kgaa pH-gesteuerte Freisetzung von Waschmittelkomponenten
US5905067A (en) * 1997-02-10 1999-05-18 Procter & Gamble Company System for delivering hydrophobic liquid bleach activators
US5955418A (en) * 1997-02-26 1999-09-21 The Procter & Gamble Company Secondary alkyl sulfate surfactant with improved solubility by kneading/extruding process
DE19709411A1 (de) 1997-03-07 1998-09-10 Henkel Kgaa Waschmittelformkörper
DE19732749A1 (de) 1997-07-30 1999-02-04 Henkel Kgaa Glucanasehaltiges Waschmittel
DE19732751A1 (de) 1997-07-30 1999-02-04 Henkel Kgaa Neue Beta-Glucanase aus Bacillus
DE19732750A1 (de) 1997-07-30 1999-02-04 Henkel Kgaa Glucanasehaltiges Reinigungsmittel für harte Oberflächen
US6992056B1 (en) 1997-12-30 2006-01-31 Henkel Kgaa Process for preparing detergent tablets having two or more regions
US6410500B1 (en) 1997-12-30 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Moulded body dishwasher detergents with soil release polymers
DE19758262A1 (de) 1997-12-31 1999-07-08 Henkel Kgaa Alkylaminotriazolhaltige, granulare Komponente für den Einsatz in Maschinengeschirrspülmitteln (MGSM) und Verfahren zu dessen Herstellung
DE19819187A1 (de) * 1998-04-30 1999-11-11 Henkel Kgaa Festes maschinelles Geschirrspülmittel mit Phosphat und kristallinen schichtförmigen Silikaten
DE19824705A1 (de) 1998-06-03 1999-12-09 Henkel Kgaa Amylase und Protease enthaltende Wasch- und Reinigungsmittel
US6057280A (en) * 1998-11-19 2000-05-02 Huish Detergents, Inc. Compositions containing α-sulfofatty acid esters and methods of making and using the same
DE19908051A1 (de) 1999-02-25 2000-08-31 Henkel Kgaa Verfahren zur Herstellung compoundierter Acetonitril-Derivate
DE19944218A1 (de) 1999-09-15 2001-03-29 Cognis Deutschland Gmbh Waschmitteltabletten
US6686327B1 (en) 1999-10-09 2004-02-03 Cognis Deutschland Gmbh & Co. Kg Shaped bodies with improved solubility in water
DE19953792A1 (de) 1999-11-09 2001-05-17 Cognis Deutschland Gmbh Waschmitteltabletten
DE19956803A1 (de) 1999-11-25 2001-06-13 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE19956802A1 (de) 1999-11-25 2001-06-13 Cognis Deutschland Gmbh Waschmitteltabletten
EG23339A (en) * 1999-12-20 2004-12-29 Procter & Gamble Bleach activators with improved solubility.
DE19962886A1 (de) 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE19962883A1 (de) 1999-12-24 2001-07-12 Cognis Deutschland Gmbh Waschmitteltabletten
DE10003124A1 (de) 2000-01-26 2001-08-09 Cognis Deutschland Gmbh Verfahren zur Herstellung von Tensidgranulaten
DE10019405A1 (de) 2000-04-19 2001-10-25 Cognis Deutschland Gmbh Verfahren zur Herstellung von Waschmittelgranulaten
US6498124B2 (en) 2000-06-02 2002-12-24 Eastman Chemical Company Isolation of phenyl ester salts from mixtures comprising sulfolane
US6660712B2 (en) * 2000-06-02 2003-12-09 Dale Elbert Van Sickle Stabilization of amido acids with antioxidants
US6500973B2 (en) 2000-06-02 2002-12-31 Eastman Chemical Company Extractive solution crystallization of chemical compounds
AU2001268171A1 (en) 2000-06-02 2001-12-11 Eastman Chemical Company Process for recycling amido-carboxylic acid esters into amido-carboxylic acids
DE60108379T2 (de) 2000-06-02 2005-12-22 Eastman Chemical Co., Kingsport Reinigung von phenylestersalzen
DE10031620A1 (de) 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Flüssigwaschmittel
MXPA03000793A (es) 2000-07-28 2003-06-04 Henkel Kgaa Enzima amilolitica novedosa, extraida de bacilo sp a 7-7 (dsm 12368) y agentes de lavado y limpiadores que contienen esta enzima amilolitica novedosa.
DE50113038D1 (de) 2000-11-28 2007-10-31 Henkel Kgaa Cyclodextrin -glucanotransferase(cg tase) aus bacillus agaradherens(dsm 9948)sowie wasch-und reinigungsmittel mit dieser neuen cyclodextrin-glucanotransferase
DE10105801B4 (de) 2001-02-07 2004-07-08 Henkel Kgaa Wasch- und Reinigungsmittel umfassend feine Mikropartikel mit Reinigungsmittelbestandteilen
DE10153792A1 (de) 2001-10-31 2003-05-22 Henkel Kgaa Neue Alkalische Protease-Varianten und Wasch- und Reinigungsmittel enthaltend diese neuen Alkalischen Protease-Varianten
DE10162728A1 (de) 2001-12-20 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii (DSM 14393) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE10162727A1 (de) 2001-12-20 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii (DSM 14391) und Wasch-und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE10163748A1 (de) 2001-12-21 2003-07-17 Henkel Kgaa Neue Glykosylhydrolasen
DE10163856A1 (de) 2001-12-22 2003-07-10 Cognis Deutschland Gmbh Hydroxymischether und Polymere in Form von festen Mitteln als Vorcompound für Wasch-, Spül- und Reinigungsmittel
DE10163884A1 (de) 2001-12-22 2003-07-10 Henkel Kgaa Neue Alkalische Protease aus Bacillus sp. (DSM 14392) und Wasch- und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE10260903A1 (de) 2002-12-20 2004-07-08 Henkel Kgaa Neue Perhydrolasen
TW200600575A (en) * 2003-12-25 2006-01-01 Kao Corp Process for producing a bleaching activator composition
US20050186271A1 (en) * 2004-02-24 2005-08-25 Sheskey Paul J. Process for dispersing a fluid in a mass of solid particles
DE102004019751A1 (de) 2004-04-23 2005-11-17 Henkel Kgaa Neue Alkalische Proteasen und Wasch- und Reinigungsmittel, enthaltend diese neuen Alkalischen Proteasen
DE102004047776B4 (de) 2004-10-01 2018-05-09 Basf Se Gegen Di- und/oder Multimerisierung stabilisierte Alpha-Amylase-Varianten, Verfahren zu deren Herstellung sowie deren Verwendung
DE102004047777B4 (de) 2004-10-01 2018-05-09 Basf Se Alpha-Amylase-Varianten mit erhöhter Lösungsmittelstabilität, Verfahren zu deren Herstellung sowie deren Verwendung
DE102005053529A1 (de) 2005-11-08 2007-06-21 Henkel Kgaa System zur enzymatischen Generierung von Wasserstoffperoxid
DE102007003143A1 (de) 2007-01-16 2008-07-17 Henkel Kgaa Neue Alkalische Protease aus Bacillus gibsonii und Wasch- und Reinigungsmittel enthaltend diese neue Alkalische Protease
DE102008000029A1 (de) 2008-01-10 2009-07-16 Lanxess Deutschland Gmbh Geschirrreinigungsmittel
DE102007003885A1 (de) 2007-01-19 2008-07-24 Lanxess Deutschland Gmbh Geschirrreinigungsmittel
DE102007016391A1 (de) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Farbschützendes Wasch- oder Reinigungsmittel
GB0710559D0 (en) * 2007-06-02 2007-07-11 Reckitt Benckiser Nv Composition
KR20100067655A (ko) * 2007-08-28 2010-06-21 다우 글로벌 테크놀로지스 인크. 세정 용도를 위한 캡슐화된 활성 성분
AU2008313803B2 (en) 2007-10-12 2014-01-30 Basf Se Dishwashing formulation comprising a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates
DE102007049830A1 (de) 2007-10-16 2009-04-23 Henkel Ag & Co. Kgaa Neue Proteinvarianten durch zirkulare Permutation
DE102007051092A1 (de) 2007-10-24 2009-04-30 Henkel Ag & Co. Kgaa Subtilisin aus Becillus pumilus und Wasch- und Reinigungsmittel enthaltend dieses neue Subtilisin
GB2473275A (en) * 2009-09-08 2011-03-09 Reckitt Benckiser Nv Bleach activator granule comprising DOBA and a process of production thereof involving extrusion
DE102015002877B4 (de) * 2015-03-09 2024-09-12 Henkel Ag & Co. Kgaa Wasch- oder reinigungsaktive Extrudate, deren Herstellung und Verwendung in granularen Wasch- oder Reinigungsmitteln

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE356700C (de) * 1918-10-09 1922-07-26 Spezialfabrik Fuer Aluminium S Verfahren zur Herstellung von Spulen aus Aluminium- oder aehnlichem Draht
US4126573A (en) * 1976-08-27 1978-11-21 The Procter & Gamble Company Peroxyacid bleach compositions having increased solubility
DE2733849A1 (de) * 1977-07-27 1979-02-15 Basf Ag Feste kaltbleichaktivatoren fuer aktivsauerstoff abgebende verbindungen enthaltende wasch- und reinigungsmittel
EP0006655B1 (fr) * 1978-06-26 1982-10-13 THE PROCTER & GAMBLE COMPANY Additif détergent sous forme de particules
ATE5896T1 (de) * 1979-11-03 1984-02-15 The Procter & Gamble Company Granulare waschmittelzusammensetzungen.
IE51848B1 (en) * 1980-11-06 1987-04-15 Procter & Gamble Bleach activator compositions,preparation thereof and use in granular detergent compositions
DE3169751D1 (en) * 1980-12-09 1985-05-09 Unilever Nv Bleach activator granules
US4399049A (en) * 1981-04-08 1983-08-16 The Procter & Gamble Company Detergent additive compositions
US4547305A (en) * 1982-07-22 1985-10-15 Lever Brothers Company Low temperature bleaching detergent compositions comprising peracids and persalt activator
GB8310080D0 (en) * 1983-04-14 1983-05-18 Interox Chemicals Ltd Bleach composition
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
DE3504628A1 (de) * 1985-02-11 1986-08-14 Henkel KGaA, 4000 Düsseldorf Verfahren zur herstellung eines rieselfaehigen granulats
US4678594A (en) * 1985-07-19 1987-07-07 Colgate-Palmolive Company Method of encapsulating a bleach and activator therefor in a binder
US5211874A (en) * 1985-08-21 1993-05-18 The Clorox Company Stable peracid and enzyme bleaching composition
US4657784A (en) * 1986-03-10 1987-04-14 Ecolab Inc. Process for encapsulating particles with at least two coating layers having different melting points
US5112514A (en) * 1986-11-06 1992-05-12 The Clorox Company Oxidant detergent containing stable bleach activator granules
DE3639115A1 (de) * 1986-11-15 1988-05-19 Henkel Kgaa Lagerbestaendiges bleichmittelgemisch mit verbessertem loesungsvermoegen
MA21216A1 (fr) * 1987-03-17 1988-10-01 Procter & Gamble Compositions de blanchiment.
GB8711153D0 (en) * 1987-05-12 1987-06-17 Warwick International Ltd Bleach activator compositions
DE3812693A1 (de) * 1988-03-19 1989-09-28 Reckitt Gmbh Reinigungstablette fuer zahnprothesen
US5049298A (en) * 1988-11-25 1991-09-17 Akzo Nv Process for the preparation of bleaching granules
US5279757A (en) * 1990-04-06 1994-01-18 Hoechst Aktiengesellschaft Stable peroxycarboxylic acid granule comprising an imidoperoxycarboxylic acid or salt thereof
GB9016504D0 (en) * 1990-07-27 1990-09-12 Warwick Int Ltd Granular bleach activator compositions
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform
GB9102507D0 (en) * 1991-02-06 1991-03-27 Procter & Gamble Peroxyacid bleach precursor compositions
DE4143016A1 (de) * 1991-12-24 1993-07-01 Henkel Kgaa Bleichaktivatoren in granulatform (ii)
US5405412A (en) * 1994-04-13 1995-04-11 The Procter & Gamble Company Bleaching compounds comprising N-acyl caprolactam and alkanoyloxybenzene sulfonate bleach activators
US5405413A (en) * 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
US5460747A (en) * 1994-08-31 1995-10-24 The Procter & Gamble Co. Multiple-substituted bleach activators

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DE69418727D1 (de) 1999-07-01
US5534196A (en) 1996-07-09
DE69418727T2 (de) 2000-03-02
ES2131803T3 (es) 1999-08-01
GR3030836T3 (en) 1999-11-30
EP0737241A1 (fr) 1996-10-16
TR27979A (tr) 1995-11-16
MA23406A1 (fr) 1995-07-01
WO1995017498A1 (fr) 1995-06-29
ATE180508T1 (de) 1999-06-15
DK0737241T3 (da) 1999-11-08

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